Mono-and dialkoxyalkyl quaternary ammonium compounds



United States Patent 3,404,183 MONO- AND DIALKOXYALKYL QUATERNARY AMMONIUM COMPOUNDS Graham K. Hughes, Minneapolis, Minn., assignor to Ashland Oil & Refining Company, Ashland, Ky., a corporation of Kentucky No Drawing. Filed Apr. 22, 1966, Ser. No. 544,415 11 Claims. (Cl. 260--567.6)

ABSTRACT OF THE DISCLOSURE Quaternary ammonium compounds useful as fabric softeners and surfactants containing as one ammonium nitrogen substituent, a long chain alkoxyalkyl group having a total of to 23 carbon and oxygen atoms and 1 to 3 oxygen atoms; a second ammonium nitrogen substituent being an alkoxyalkyl group as described above, or an alkyl group having 15 to 23 carbon atoms; and the remaining two ammonium substituents being lower alkyl groups.

The present invention relates to novel quaternary ammonium compounds and to methods for their preparation. The novel quaternary ammonium compounds are useful as surfactants and are of particular value as fabric softeners.

The quaternary ammonium compounds of the present invention have the general formula:

in which R and R are the same or different lower alkyl radicals having from 1 to 4 carbon atoms; X is an anion and preferably a halogen having an atomic weight of 35.5 to 127; R is a monovalent radical in which the sum of oxygen and carbon atoms is from 14 to 22 and preferably from 16 to 18 and which has the formula:

(II) R R R-o-orr (31rin which R is an alkyl radical or an alkoxyalkyl radical containing up to two oxyalkylene groups of 2 to 3 carbon atoms, and R" is hydrogen or methyl and can be the same or different; and wherein R is R or an alkyl radical of 14 to 22 carbon atoms and preferably 16 to 18 carbon atoms. The preferred quaternary ammonium compounds of the present invention have the formula:

1?]! 3;!!! [(R'Q-CH-CH-CH2)2N(R2)2][Y] wherein R R, and R" are as defined and Y is a halogen having an atomic weight of 35.5 to 127.

The quaternary ammonium compounds of the present invention can be prepared by a process employing the following reactions:

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The cyanoalkylation of the alcohol (Reaction A) is carried out in the liquid phase at atmospheric pressure and at temperatures between 0 to 100 C. and preferably between 50 to C. Although inert solvents can be employed, it is, in general, preferable to carry out the reaction in bulk. Catalytic concentrations of an alkali metal, e.g., 0.01 to 1.0% by weight of the alcohol, are dissolved in the alcohol by heating to temperatures of to C. The mixture is cooled to about 50 to 55 C. and the ethylenically unsaturated nitrile is added slowly to the alcohol at a rate such that the reaction temperature does not rise substantially above 70 C. The amount of the ethylenically unsaturated nitrile employed is generally slightly in excess, e.g., 5 to 20% over the stoichiometric amount of nitrile required. On complete addtiion of the nitrile, the reaction is preferably permitted to stand for 6 to 20 hours, which results in higher yields of the ether nitrile. The alkali metal is then neutralized and the ether nitrile distilled out of the reaction mixture. A high yield of the pure ether nitrile is obtained.

The ether nitrile is then hydrogenated to the amine, employing hydrogenation techniques heretofore developed for the hydrogenation of nitriles. Particularly preferred is the hydrogenation of the ether nitrile with a Raney nickel or palladium catalyst. The hydrogenation is normally conducted as a two-step process. In the first step, the nitrile is converted to a primary amine in the presence of NH In the second step, the amine is sparged with hydrogen and converted to the secondary amine which can contain minor concentrations of tertiary amine. Instead of hydrogenating just the ether nitrile, a mixture of the ether nitrile and a nitrile having the formula R CN, wherein R has the above-indicated meaning, can be reacted together to form a mixed secondary amine. The secondary amine is then reacted with a lower alkyl halide to result in the quaternary ammonium compound. The quaternization of the amine is a well-known reaction and thus requires no further detailed description. Minor quantities of tertiary amine formed together with the secondary amine are converted along with the secondary amine to a quaternary ammonium compound. The quaternary ammonium compounds derived from the tertiary amines do not deleteriously affect the utility of the quaternary ammonium compound derived from the secondary amine and hence separation of the secondary and tertiary amines formed in the hydrogenation step is unnecessary. The separation of such would significantly add to the cost of producing the novel quaternary ammonium compounds of the present invention.

Alcohols which can be employed to form the novel quaternary ammonium compounds of the present invention include: decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, branched hexadecanol, secondary decanol, secondary pentadecanol, ethoxylated dodecanol, propoxylated dodecanol, diethoxylated octanol, dipropoxylated octanol, diethoxylated decanol, and dipropoxylated decanol. Mixtures of these and other alcohols can be employed and commercially available alcohol cuts such as are produced by the 0x0 process or the Ziegler method are valuable alcohols for the preparation of the novel quaternary ammonium compounds. The unsaturated nitriles employed include acrylonitrile, methacrylonitrile, and crotononitrile. The secondary amines are reacted with such lower alkyl halides as: methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, and butyl chloride.

The novel quaternary ammonium compounds of the present invention are surfactants and are particularly useful as fabric softeners. In addition to imparting a soft, fluffy feel to textile fabrics when used in concentrations normal for fabric softeners, the novel quaternary ammonium compounds can be handled, shipped, and stored in liquid form without requiring excessive amounts of diluent, disperse more readily in water particularly cold water than fabric softeners heretofore developed, form clear fluid dispersions, and exhibit a higher degree of compatability with salts and anionic detergents than obtained with fabric softeners heretofore developed.

The formation and the utility of the novel quaternary ammonium compounds of the present invention are further illustrated by the following examples in which all units of quantity are by weight unless otherwise indicated.

Example 1 (A) Into a reaction flask equipped with dropping funnel, agitator and thermometer is charged 828 g. of a C to C alcohol mixture, and 0.83 g. of sodium. The mixture is heated to 95 C. with agitation until the sodium has dissolved. The solution is then cooled down to 55 C. and the addition of 223.0 g. of acrylonitrile started. The addition is continued for a period of 90 minutes While the temperature is maintained at 55 to 60 C. On completion of the addition, agitation of the reaction mixture is continued for another hour. The reaction mixture is then neutralized by the addition of 2.15 g. of acetic acid and filtered. The reaction product is distilled at 150 to 190 C. and 0.2 mm. Hg pressure, to result in 930 g. of C C -alkoxyethylnitrile.

(B) Into a 2-liter Parr bomb is charged 600 g. of the C C -alkoxyethylnitrile and 24 g. of a commercially available nickel hydrogenation catalyst, Girdler G 49-B. The reaction mixture is purged, heated to 100 F. and pressured to 100 p.s.i. with NH The reaction vessel is then heated to 290 F. and pressured to 550 p.s.i. with hydrogen. The mixture is agitated at a temperature of 290 to 300 F. and maintained at such pressure by feeding additional hydrogen for a period of three hours until all of the nitrile has been converted to primary amine. The reaction mixture is then sparged with hydrogen for an additional hour while heating to 350 F. to 50 p.s.i., thereby converting the primary amine to secondary amine. On venting and filtering, there is obtained a liquid product comprising mainly di(alkoxypropyl)amine in which the alkoxy group contains from 12 to 15 carbon atoms and a minor proportion of the corresponding tri(alkoxypropyl) amine.

(C) Into the same Parr bomb is charged 434 g. of the product of Reaction B, 124 g. of isopropanol, 34 g. of water, and 110 g. of sodium carbonate. The reaction vessel is heated to 212 F. and pressured to 95 p.s.i. with methyl chloride. The reaction mixture is cooled and vented, and additional methyl chloride is charged up to the same pressure. The venting and charging of methyl chloride is repeated until no further methyl chloride is absorbed by the mixture. The reaction mixture is then cooled to room temperature and filtered. The resulting product is liquid and contains about 75% of di(alkoxypropyl)dimethyl ammonium chloride in which the alkoxy group has from 12 to 15 carbon atoms.

The quaternary ammonium compound is readily dispersed in cold Water and when employed at a 0.1% level in the rinse water of a washing machine cycle, improves the flufliness and softness of towels to a greater extent than similarly treated towels employing a commercially available fabric softener.

The quaternary ammonium compound is further tested for compatability with zinc nitrate used in textile applications by mixing equal amounts of a 5% dispersion of the quaternary ammonium compound in water with a 5% zinc nitrate solution. The quaternary ammonium compound can be maintained in the mixture in the form of a dispersion with slight agitation without forming a.precipitate.

4 Example 2 Into a 2-liter Parr bomb is charged 325 g. of alkoxyethylnitrile in which the alkoxy group contains from 12 to 15 carbon atoms, 325 g. of hard tallow nitrile, and 26.0 g. of a nickel hydrogenation catalyst commercially available as Girdler G 49-B. The reaction vessel is purged, heated to 100 F. and pressured to 100 p.s.i. with NH and then heated to 290 F. and pressured with hydrogen to 510 p.s.i. The reaction is agitated and maintained at that pressure and a temperature of 290 to 300 F. for about one hour. The reaction mixture is then vented, heated to 350 F. and sparged with hydrogen at a pressure of 50 p.s.i. for another 90 minutes. On cooling to 200 F., venting of the reaction vessel, and filtering of the reaction mixture, there is obtained as the principal product alkoxypropyloctadecylamine in which the alkoxy group contains from 12 to 15 carbon atoms.

Into the same Parr bomb is then charged 400 g. of the amine, 118 g. of isopropanol, 30 g. of H 0, and 100 g. of sodium carbonate. The reaction mixture is heated to 212 F. and pressured to 100 p.s.i. with methyl chloride. The reaction gases are then vented. Recharging and venting of the reaction mixture is repeated until no further methyl chloride is absorbed by the reaction mixture. The resulting product is filtered and a solution containing of quaternary ammonium compound, of which the major proportion is alkoxypropyloctadecyldimethyl ammonium chloride, in which the alkoxy group contains from 12 to 15 carbon atoms, is obtained.

Employing the liquid quaternary ammonium compound in the rinse water of a washing machine cycle as described in Example 1, towels of a higher degree of flufiiness and softness are obtained than when commercially available fabric softeners are employed in the same washing machine cycle.

Example 3 (A) Into a reaction flask equipped with dropping funnel, agitator and thermometer is charged 800 g. of tridecyl alcohol and 0.8 g. of sodium. The mixture is heated to C. with agitation until the sodium has dissolved. The solution is then cooled down to 56 C. and the addition of 223 g. of acrylonitrile started. The addition is continued for a period of about one hour while the temperature is maintained at 55 to 60 C. On completion of the addition, agitation of the reaction mixture is continued for another hour. The reaction mixture is then neutralized by the addition of 2.1 g. of acetic acid, and filtered. The reaction product is distilled over at 160 to 210 C. and a pressure of 0.1 mm. Hg to result in 880 g. of tridecyloxyethyl nitrile.

(B) Into a 2-liter Parr bomb is charged 880 g. of the nitrile and 35 g. of a commercially available nickel hydrogenation catalyst, Girdler G 49-B. The reaction vessel is purged, pressured to p.s.i. with NH at 100 F., and then heated to 290 F. and pressured to 510 p.s.i. with hydrogen. Agitation is continued at that temperature and pressure for about two hours. The gases are vented off and the temperature is increased to 35 0 F. and the reaction mixture is sparged with hydrogen for an additional two hours. The reaction vessel is vented and the reaction mixture is filtered to result in di(tridecyloxypropyl)amine and a minor proportion of the corresponding tertiary amine.

(C) Into the same Parr bomb is charged 425 g. of the amine, 100 g. of sodium carbonate, 124 g. of isopropanol, and 31 g. of water. The reaction vessel is then charged with methyl chloride until at 95 F. a pressure of 35 p.s.i. is obtained. The temperature is raised to 212 F., causing the pressure to rise to 125 p.s.i. The reaction mixture is then cooled to 90 F., vented, and recharged with methyl chloride to 45 p.s.i. The temperature is raised to 212 F. The venting and charging step is repeated a third time. The resulting product. on filtration, is a 75% solution of quaternary ammonium compounds containing a major proportion of di(tridecyloxypropyl)dimethyl ammonium chloride.

The quaternary ammonium compound is readily dispersible in water at concentration levels of 5%, forms clear solutions at the 40% level, and does not freeze at temperatures above 40 F.

Example 4 Following the procedure of Example 3, diethoxylated C to C aliphatic alcohol is reacted with acrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkyldiethoxypropyl)dimethyl ammonium chloride, in which the alkyl groups have from 8 to 10. carbon atoms.

Example 5 Following the procedure of Example 3, a mixture of C and C straight chain alcohol (commercially available as Alfol 1214) is reacted with methacrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkoxy-Z-methylpropyl)dimethyl ammonium chloride in which the alkoxy groups have 12 and 14 carbon atoms.

Example 6 Following the procedure of Example 3, a mixture of dipropoxylated C to C alcohols, in which the alcohols are derived from coconut oil, is reacted with acrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkyldipropoxypropyl)dimethyl ammonium chloride, in which the alkyl groups have from 8 to 10 carbon atoms.

Example 7 The procedure of Example 3(C) is repeated, employing ethyl bromide instead of methyl chloride, and di(tridecyloxypropyl)diethyl ammonium bromide is obtained.

The foregoing examples have illustrated the preparation of the novel quaternary ammonium compounds of the present invention. It will be apparent that other quaternary ammonium compounds within the scope of the present invention can be similarly prepared by the described methods. Alternate methods or modified procedures of preparing the novel quaternary ammonium compounds will be apparent to those skilled in the art.

The quaternary ammonium halides illustrated in the examples are readily converted to hydroxides, sulfates, nitrates, phosphates, acetates, formates, and sulfonates by metathesis reactions employing techniques heretofore developed in the art.

It is to be understood that the utility of the quaternary ammonium compounds is not limited to their use as fabric softeners as illustrated in the examples and that the quaternary ammonium compounds have utility in a wide range of applications based on their surfactant properties.

where R and R are lower alkyl radicals having 1 to 4 carbon atoms; X is an anion selected from the group consisting of halogen, hydroxide, sulfate, nitrate, phosphate, acetate, formate and sulfonate; R is a monovalent radical in which the sum of oxygen and carbon atoms is from 14 to 22, and which has the formula:

in which R 'is an alkyl or an alkoxyalkyl radical con- 7 taining up to two oxyalkylene groups of 2 to 3 carbon atoms, and R" is hydrogen or methyl; and wherein R is R or an alkyl radical of 14 to 22 carbon atoms.

2. Quaternary ammonium compounds of claim 1 wherein R is said alkyl radical.

3. Quaternary ammonium compounds of claim 1 wherein R is said alkyl radical and R is said alkyl radical.

4. Quaternary ammonium compounds of claim 1 where R is said alkyl radical and R is said alkoxyalkyl radical.

5. Quaternary ammonium compounds of claim 1 wherein R, is said R radical.

6. Quaternary ammonium compounds of claim 1 wherein R is said R radical and R is said alkyl.

7. Quaternary ammonium compounds of claim 1 wherein R is said R radical and R is said alkoxyalkyl radical.

8. Quaternary ammonium compounds of claim 1 whereinX is chlorine and R and R are methyl.

9. The quaternary ammonium compounds of claim 1 wherein R is R, R is an alkyl radical of 12 to 15 carbon atoms, both R are hydrogen, and R and R are methyl.

.10. The quaternary ammonium compounds of claim 9 in which R is an alkyl radical of 13 carbon atoms.

11. The quaternary ammonium compounds of claim 1 wherein R is R, R is an alkyl diethoxy radical in which said alkyl group contains 8 to 10 carbon atoms, both R" are hydrogen, and R and R are methyl.

References Cited UNITED STATES PATENTS 2,087,132 7/1937 Taub et al. 260-567.6 X 2,810,720 10/1957 Lane 260567.6 X 2,810,721 10/1957 Lane 260567.6 X

OTHER REFERENCES The Chemistry of Acrylonitrile, pp. 17 and 24. Organic Synthesis, Migrdichian, volume 1, p. 439. Synthetic Organic Chemistry, Wagner and Zook, p. 668.

CHARLES B. PARKER, Primary Examiner.

S. T. LAWRENCE III, Assistant Examiner. 

